CN107629191A - Epoxy-ester prepolymer, preparation method and the water-base epoxy of preparation ester resin and method - Google Patents
Epoxy-ester prepolymer, preparation method and the water-base epoxy of preparation ester resin and method Download PDFInfo
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Abstract
Epoxy-ester prepolymer, preparation method and the water-base epoxy of preparation ester resin and method, the epoxy-ester prepolymer include bisphenol A epoxide resin, dicyclopentadiene dimethanol diglycidyl ether, terpinum diglycidyl ether, drying oil fatty acid, semi-drying oil aliphatic acid, saturated fat acid anhydrides, unsaturated fat acid anhydrides, esterification catalyst and organic solvent.The invention also discloses its preparation method.The water-base epoxy ester resin includes vinyl monomer, initiator, epoxy-ester prepolymer, cosolvent, nertralizer and the water.The invention also discloses its preparation method.Epoxy-ester prepolymer weather resistance of the present invention is excellent, rate of drying is fast, impact strength is high；Water-base epoxy ester resin of the present invention all increases significantly on glass transition temperature, antiseptic property and bin stability, can be not only used for anti-corrosion primer and can and is used to protect finish paint；Preparation method technique of the present invention simply, stably, is suitable for industrialized production.
Description
Technical field
The present invention relates to the water-base epoxy ester resin and method of a kind of epoxy-ester prepolymer, preparation method and preparation, specifically
It is related to a kind of epoxy-ester prepolymer, preparation method and the one pack system of preparation self-drying paint water-base epoxy ester resin and method.
Background technology
Epoxy ester resin generally has excellent caking property, salt fog resistance and good from dryness, but weather resistance is poor；
And water-base epoxy ester resin easily hydrolyzes under alkaline environment, the bin stability of coating is influenceed.Vinyl modified ring
Oxygen ester improves the bin stability of coating and the weather resistance of film, but slow from dry speed, and hardness of film development is slow, influences to apply
Work efficiency rate；And gloss is low without being suitable as finish paint.
CN101717490A discloses a kind of rosin-modified epoxy ester resin and preparation method, is by epoxy resin and toughness reinforcing
Agent, chain extender, the reaction of unrighted acid rosin form.Although prepared epoxy ester resin has higher glassy state temperature
Degree, fast drying, and there is good mechanical performance and excellent chemical mediator-resitant property, it can be used as the film forming matter of corrosion resistant coating.
But rosin complicated component, quality are unstable so that the quality of prepared epoxy ester resin is difficult to control, and program institute
Resin weather resistance processed is poor, is not suitable for finish paint.
CN102391439A discloses ester modified aqueous alkide resin of a kind of epoxy and preparation method thereof, including：Alkyd
The preparation of resin, the synthesis of epoxy-ester and the synthesis of epoxy-ester modified alkyd resin, be by mass ratio be 0.2:1~0.5:1
Epoxy-ester is stirred with basic alkyd, 1~3 part of organic tin catalyst, 5~15 parts of dimethylbenzene, anti-in 180 DEG C of backflows
1~2h is answered, until when the acid number measured is less than 7mgKOH/g；Also include the Water-borne modification of modified alkyd resin.This method institute
Product both to have maintained paint dryness, glossiness, durability, pliability, hardness and the preferable dissolubility of alkyd resin etc. excellent
Performance, there is the excellent caking property of epoxy-ester, salt fog resistance and good from dryness again, it is excellent resistance to molten to can guarantee that film has
Agent and chemical resistance.But the program is not suitable for aqueous coating system, reason is the alkaline bar after Water-borne modification
Part can cause alkyd resin to be hydrolyzed with epoxy ester resin, so as to cause bin stability to be deteriorated.
CN104479087A discloses a kind of quick-dry type water-base epoxy ester emulsion and its preparation method and application, is by epoxy
The acid value of resin, vegetable oil, the unrighted acid of 2/3 mass parts through high temperature esterification to design, adds remaining 1/3
The unrighted acid of mass parts, epoxy ester resin is made, then vinyl monomer is added dropwise and the mixture of initiator is modified；
Cooling adds cosolvent, nertralizer after completion of the reaction, is finally diluted with deionized water.Although the resin can be used for anti-corrosive primer,
But vegetable oil used belongs to fatty glyceride, it is impossible to is reacted with epoxy resin, addition can only occur with unrighted acid
Reaction, process are difficult to control, and gel easily occurs.
CN106674441A discloses a kind of water-soluble acrylic modified epoxy ester resin and preparation method thereof, and being will be organic
Si modification epoxy-ester prepolymer carries out graft copolymerization with vinyl monomer.But the resin contains silicon materials so that is made
Coating film forming after surface energy it is relatively low, thus recoat poor performance, be only applicable to protect finish paint.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of weatherability
The epoxy-ester prepolymer that energy is excellent, rate of drying is fast, impact strength is high.
Further technical problem to be solved of the invention is to overcome drawbacks described above existing for prior art, there is provided a kind of
Technique simply, stably, is suitable for the preparation method of the epoxy-ester prepolymer of industrialized production.
Present invention technical problem further to be solved is to overcome drawbacks described above existing for prior art, there is provided one
Kind dried coating film speed is fast, hardness of film development is fast, antiseptic property is excellent, coating film gloss is high, can be not only used for anti-corrosion primer and can
For protecting the water-base epoxy ester resin of finish paint.
Further technical problems to be solved of the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of
Technique simply, stably, is suitable for the preparation method of the water-base epoxy ester resin of industrialized production.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of epoxy-ester prepolymer, includes bisphenol-A ring
Oxygen tree fat, dicyclopentadiene dimethanol diglycidyl ether, terpinum diglycidyl ether, drying oil fatty acid, semi-drying
Fatty acid oil, saturated fat acid anhydrides, unsaturated fat acid anhydrides, esterification catalyst and organic solvent.Bisphenol A epoxide resin and terpene two
Alcohol diglycidyl ether, be advantageous to improve the antiseptic property of product；Dicyclopentadiene dimethanol diglycidyl ether, terpinum
Diglycidyl ether is advantageous to improve the glass transition temperature of resin film forming matter with drying oil fatty acid, accelerates the rate of drying of film
With hardness development speed；Dicyclopentadiene dimethanol diglycidyl ether, terpinum diglycidyl ether and aliphatic acid help
In the weather resistance of reinforced resin film；Aliphatic acid, saturated fat acid anhydrides are favorably improved the gloss of resin coating film.
Preferably, the parts by weight of the epoxy-ester prepolymer each component are：155~175 parts of bisphenol A epoxide resin, dimerization
10~30 parts of cyclopentadiene dimethanol diglycidyl ether, 10~30 parts of terpinum diglycidyl ether, drying oil fatty acid 95
~105 parts, 95~105 parts of semi-drying oil aliphatic acid, 1~5 part of saturated fat acid anhydrides, 1~3 part of unsaturated fat acid anhydrides, esterification
0.10~0.30 part of catalyst, 170~210 parts of organic solvent.
Preferably, the bisphenol A epoxide resin is in E-51 types, E-44 types, E-20 types or E-12 type epoxy resin etc.
It is one or more of.
Preferably, the drying oil fatty acid be linoleic acid, linolenic acid, eleostearic acid, high iodine number ready denier oil acid or
One or both of dehydrated castor oil fatty acid etc..The iodine number scope of the high iodine number ready denier oil acid is 150~160.
Preferably, the semi-drying oil aliphatic acid is soya fatty acid and/or low iodine number ready denier oil acid etc..It is described
The iodine number scope of low iodine number ready denier oil acid is 120~135.
Preferably, the saturated fat acid anhydrides is one kind in HHPA, methyl hexahydrophthalic anhydride or carbic anhydride etc.
It is or several.
Preferably, the unsaturated fat acid anhydrides is maleic anhydride and/or fumaric acid anhydride etc..
Preferably, the esterification catalyst is zinc oxide or normal-butyl tin oxide etc..
Preferably, the organic solvent is one kind or several in propylene glycol monomethyl ether, propylene glycol propyl ether or propandiol butyl ether etc.
Kind.
Technical scheme is as follows used by the present invention further solves its technical problem：A kind of preparation of epoxy-ester prepolymer
Method, by bisphenol A epoxide resin, dicyclopentadiene dimethanol diglycidyl ether, terpinum diglycidyl ether, drying oil
Aliphatic acid and semi-drying oil aliphatic acid mix, and carry out first time heating response, after cooling, add saturated fat acid anhydrides,
Unsaturated fat acid anhydrides and esterification catalyst mix, and carry out second of heating response, cooling, are eventually adding organic solvent,
.The existing addition esterification of preparation process of epoxy-ester prepolymer, also there is a condensation esterification, and addition esterification mistake
Journey does not generate water, is easy to carry out, and is advantageous to shorten technological process.
Preferably, the temperature of the first time heating response is 180~200 DEG C, and the time is 1~3h.
Preferably, after first time heating response, 145~155 DEG C are cooled to.
Preferably, the temperature of second of heating response is 190~210 DEG C, reacts to acid number≤10mgKOH/g and is
Only.
Preferably, after second of heating response, 80~100 DEG C are cooled to.
Technical scheme is as follows used by the present invention further solves its technical problem：A kind of water-base epoxy ester resin,
Include vinyl monomer, initiator, epoxy-ester prepolymer, cosolvent, nertralizer and the water.Epoxy-ester prepolymer can strengthen tree
The antiseptic property of fat is without influenceing bin stability energy；The acrylic acid tree that the graft copolymerization of vinyl monomer and the prepolymer is formed
Fat part, the ester bond of epoxy ester resin is protected by coating function, significantly improves the bin stability of resin, and contain nitro
Vinyl monomer can cause resin coating film that there is more preferable hardness and antiseptic property；Initiator can promote vinyl monomer and ring
The graft polymerization reaction of oxygen ester；Cosolvent belongs to hydrophilic organic solvent, can improve the dissolution degree of resin, has faint
Emulsification, improve the bin stability of resin；Nertralizer causes resin is neutralized into salt to obtain water solubility.
Preferably, the parts by weight of the water-base epoxy ester resin each component are：200~260 parts of vinyl monomer（More preferably
220~240 parts）, 18~26 parts of initiator（More preferably 19~22 parts）, 500~550 parts of the epoxy-ester prepolymer（More preferably
510~540 parts）, 95~105 parts of cosolvent（More preferably 96~102 parts）, 10~20 parts of nertralizer（More preferably 12~19 parts）、
770~790 parts of water（More preferably 772~780 parts）.If the dosage of the vinyl monomer is excessive, a large amount of vinyl monomers with
Unsaturated double-bond in epoxy-ester prepolymer reacts, and manufactured molecular resin amount is larger, viscosity dramatically increases, production technology
It is unmanageable, it may occur however that gel, and if the dosage of vinyl monomer is very few, graft copolymer is not enough to main chain ester bond shape
Into protective effect, the bin stability of resin will be influenceed, and molecular resin amount is too low, under the rate of drying for causing made coating
Drop；If the dosage of the initiator is excessive, it is unfavorable for controlling of production process, is unfavorable for the Color Quality control of resin, and draws
Hair agent decompose after residuals coating can be had undesirable effect, and if the dosage of initiator is very few, vinyl monomer connects
The conversion ratio of branch copolyreaction is relatively low, causes molecular resin amount relatively low, influences resin rate of film build and dry film hardness；The epoxy
If the dosage of ester prepolymer is very few, the antiseptic property of made film is difficult to be effectively ensured, and the use of epoxy-ester prepolymer
If amount is excessive, the graft polymers that the vinyl monomer being introduced into is formed is difficult to form effective cladding to the ester bond in epoxy-ester
And protective effect；If the cosolvent dosage is excessive, the gloss for causing made film is declined, initial stage, water resistance was deteriorated, and
If the dosage of cosolvent is very few, resin bin stability and filming performance can be influenceed；If the dosage of the nertralizer is excessive,
It will then cause resin viscosity to significantly increase, and influence the dilution rate that is watered during with paint, and the nertralizer remained can make made film
Water resistance at initial stage decline, and if the dosage of nertralizer is very few, the water-soluble deficiency of resin.
Preferably, the vinyl monomer includes styrene, methacrylic acid, methyl methacrylate, polyethylene glycol first
Base acrylate and the vinyl monomer of nitro substitution, its mass ratio mixed are 96~126:12~38:45~75:21~
39:6~12（More preferably 100~120:15~35:50~60:25~35:8~10）.The polyethylene glycol methacrylate-styrene polymer
Introducing cause water-base epoxy ester resin that there is certain automatic emulsifying performance, be easy to the appropriate use for reducing methylpropanoic acid acid monomers
Amount, can be with the water resistance at initial stage of film with the bin stability of reinforced resin；The vinyl monomer of the nitro substitution can carry
Rise hardness development speed, the enhancing antiseptic property of water-base epoxy ester resin coating film.
Preferably, in the polyethylene glycol methacrylate-styrene polymer, the relative molecular weight of polyethylene glycol segment is 300~800
（More preferably 350~600）.
Preferably, the vinyl monomer of nitro substitution is 2 methyl 2 nitropropyl methacrylate and/or right
Nitrostyrolene etc..
Preferably, the initiator is benzoyl peroxide, peroxybenzoate or lauroyl peroxide etc.
In one or more.
Preferably, the cosolvent is isopropanol, n-butanol, propylene glycol monomethyl ether, propylene glycol propyl ether, propandiol butyl ether, two
One or more in propandiol butyl ether or methyl iso-butyl ketone (MIBK) etc..
Preferably, the nertralizer is the one or more in ammoniacal liquor, triethylamine, dimethylethanolamine or meglumine etc..
Technical scheme is as follows used by the present invention further solves its technical problem：A kind of water-base epoxy ester resin
Preparation method, comprise the following steps：
（1）Under reaction system reflux state, by vinyl monomer and the mixed liquor of a part of initiator, the epoxy is added drop-wise to
In the mixed solution of ester prepolymer and a part of cosolvent, after being added dropwise to complete, insulation reaction, then be added dropwise remainder initiator and
The mixed solution of remainder cosolvent, after being added dropwise to complete, insulation reaction, cooling, obtain acrylic modified epoxy ester resin；
（2）In step（1）Nertralizer is added in gained acrylic modified epoxy ester resin, after stirring, adds water, obtains water-based ring
Oxygen ester resin.
Step（1）The acid number of gained acrylic modified epoxy ester resin is 22~36mgKOH/g, and solid is divided into 78~82%.
Step（2）The solid of gained water-base epoxy ester resin is divided into 38~42%, and pH value is 7.5~9.0.Gained resin exists
Under the acid number, it is ensured that resin has enough water solubilitys, is easy to add water latting drown in work progress；Gained resin is described solid
Under body point, it is ensured that there is enough film forming matters in resin.
Preferably, step（1）In, the temperature of the backflow is 110~130 DEG C.Cosolvent belongs to hydrophilic organic molten
Agent, backflow is contributed to radiate in synthesis technique.
Preferably, step（1）In, the speed being added dropwise twice is 200~300kg/h.Under the rate of addition, more have
Beneficial to elimination residual monomer.
Preferably, step（1）In, the time of insulation reaction is 1~2h twice.Within the time of the insulation reaction more
Be advantageous to eliminate residual monomer.
Preferably, step（1）In, the mass ratio for the initiator being successively added dropwise is 3.5~4.5:1.
Preferably, step（1）In, the mass ratio of the remainder initiator and remainder cosolvent is 1:6~12
（More preferably 1:7~9）.It is highly preferred that the remainder initiator in rear addition is liquid；In the remainder hydrotropy of rear addition
Agent is propylene glycol monomethyl ether and/or methyl iso-butyl ketone (MIBK).The purpose for adding initiator is the residual monomer in elimination reaction system, is gone
Eliminate the unusual smell, be advantageous to the stabilization of resin, be easy to the use of user.
Preferably, step（1）In, it is cooled to 50~60 DEG C.
Beneficial effects of the present invention are as follows：
（1）Artificial weathering aging time >=110h of epoxy-ester prepolymer of the present invention, surface drying time≤30min, anti-forward impact
The kgcm of intensity >=50-1, illustrate that its weather resistance is excellent, rate of drying is fast, impact strength is high；
（2）Glass transition temperature >=67 DEG C of water-base epoxy ester resin of the present invention, resisting salt fog corrosion time >=168h, bin stability
>=12 months, combination property was better than commercially available water-base epoxy ester resin, illustrate water-base epoxy ester resin of the present invention glass transition temperature,
All increased significantly on antiseptic property and bin stability, can be not only used for anti-corrosion primer and can and be used to protect finish paint；
（3）The preparation method of epoxy-ester prepolymer of the present invention and the preparation method technique of water-base epoxy ester resin simply, stably, are fitted
It is suitable for industrialized production.
Embodiment
With reference to embodiment, the invention will be further described.
High iodine number ready denier oil acid used in the embodiment of the present invention is commercially available, iodine number 156, used low iodine number
Ready denier oil acid is commercially available, iodine number 128；In used polyethylene glycol methacrylate-styrene polymer, the phase of polyethylene glycol segment
It is 400 to molecular mass；Chemical reagent used in the embodiment of the present invention, unless otherwise specified, pass through routine business approach
Obtain.
Epoxy-ester prepolymer embodiment 1~3
The dosage of 1~3 each raw material of epoxy-ester prepolymer embodiment is as shown in table 1：
1 epoxy-ester prepolymer embodiment of table, 1~3 each raw material uses scale
Note："-" represents to be not added with table.
The preparation method embodiment 1 of epoxy-ester prepolymer
According to quality described in 1 embodiment of table, 1 each raw material, by bisphenol A epoxide resin, dicyclopentadiene dimethanol 2-glycidyl
Ether, terpinum diglycidyl ether, drying oil fatty acid and semi-drying oil aliphatic acid mix, and at 200 DEG C, carry out first
Secondary heating response 1.5h, after being cooled to 150 DEG C, add saturated fat acid anhydrides, unsaturated fat acid anhydrides and esterification catalyst and mix
Stirring is closed, at 200 DEG C, when carrying out second of heating response to acid number ＜ 10mgKOH/g, 80 DEG C is cooled to, has been eventually adding
Solvent, obtain epoxy-ester prepolymer A1.
The preparation method embodiment 2 of epoxy-ester prepolymer
According to quality described in 1 embodiment of table, 2 each raw material, by bisphenol A epoxide resin, dicyclopentadiene dimethanol 2-glycidyl
Ether, terpinum diglycidyl ether, drying oil fatty acid and semi-drying oil aliphatic acid mix, and at 190 DEG C, carry out first
Secondary heating response 2h, after being cooled to 155 DEG C, add saturated fat acid anhydrides, unsaturated fat acid anhydrides and esterification catalyst mixing
Stirring, at 195 DEG C, when carrying out second of heating response to acid number ＜ 10mgKOH/g, 90 DEG C are cooled to, is eventually adding organic
Solvent, obtain epoxy-ester prepolymer A2.
The preparation method embodiment 3 of epoxy-ester prepolymer
According to quality described in 1 embodiment of table, 3 each raw material, by bisphenol A epoxide resin, dicyclopentadiene dimethanol 2-glycidyl
Ether, terpinum diglycidyl ether, drying oil fatty acid and semi-drying oil aliphatic acid mix, and at 185 DEG C, carry out first
Secondary heating response 3h, after being cooled to 146 DEG C, add saturated fat acid anhydrides, unsaturated fat acid anhydrides and esterification catalyst mixing
Stirring, at 210 DEG C, when carrying out second of heating response to acid number ＜ 10mgKOH/g, 95 DEG C are cooled to, is eventually adding organic
Solvent, obtain epoxy-ester prepolymer A3.
It is strong to the weather resistance, rate of drying and shock resistance of epoxy-ester prepolymer embodiment 1~3 according to national standard detection method
Degree is detected, as a result as shown in table 2.
The performance test results table of 2 epoxy-ester prepolymer embodiment of table 1~3
As shown in Table 2, artificial weathering aging time >=110h of epoxy-ester prepolymer embodiment 1~3 of the present invention, surface drying time≤
30min, the kgcm of anti-forward impact intensity >=50-1, illustrate epoxy-ester prepolymer weatherability of the present invention is excellent, rate of drying is fast,
Impact strength is high.
Water-base epoxy ester Resin Example 1~3
The dosage of 1~3 each raw material of water-base epoxy ester Resin Example is as shown in table 3：
3 water-base epoxy ester Resin Example of table, 1~3 each raw material uses scale
Note："-" represents to be not added with table；Wherein, initiator 1, initiator 2 distinguish method for expressing embodiment step（1）Middle priority
The initiator amount of addition；Cosolvent 1, cosolvent 2 distinguish method for expressing embodiment step（1）The cosolvent that middle priority adds is used
Amount.
The preparation method embodiment 1 of water-base epoxy ester resin
（1）According to quality described in 3 embodiment of table, 1 each raw material, in the case where temperature of reaction system is 120 DEG C of reflux states, by vinyl
The mixed liquor of monomer and initiator 1, the mixed solution of epoxy-ester prepolymer A1 and cosolvent 1 is added drop-wise to 260kg/h speed
In, after being added dropwise to complete, insulation reaction 1h, then with 220kg/h speed dropwise addition initiator 2 and the mixed solution of cosolvent 2, be added dropwise
After the completion of, insulation reaction 1h, 50 DEG C are cooled to, obtains acrylic modified epoxy ester resin；
（2）According to quality described in 3 embodiment of table, 1 each raw material, in step（1）In being added in gained acrylic modified epoxy ester resin
And agent, after stirring, add water, obtain water-base epoxy ester resin B 1.
After testing, step（1）The acid number of gained acrylic modified epoxy ester resin is 23mgKOH/g, and solid is divided into 78%；
Step（2）The solid of gained water-base epoxy ester resin B 1 is divided into 40%, pH value 7.9.
The preparation method embodiment 2 of water-base epoxy ester resin
（1）According to quality described in 3 embodiment of table, 2 each raw material, in the case where temperature of reaction system is 115 DEG C of reflux states, by vinyl
The mixed liquor of monomer and initiator 1, the mixed solution of epoxy-ester prepolymer A2 and cosolvent 1 is added drop-wise to 210kg/h speed
In, after being added dropwise to complete, insulation reaction 1.5h, then with 280kg/h speed dropwise addition initiator 2 and the mixed solution of cosolvent 2, drop
After the completion of adding, insulation reaction 1.5h, 55 DEG C are cooled to, obtains acrylic modified epoxy ester resin；
（2）According to quality described in 3 embodiment of table, 2 each raw material, in step（1）In being added in gained acrylic modified epoxy ester resin
And agent, after stirring, add water, obtain water-base epoxy ester resin B 2.
After testing, step（1）The acid number of gained acrylic modified epoxy ester resin is 26mgKOH/g, and solid is divided into
79.1%；Step（2）The solid of gained water-base epoxy ester resin B 2 is divided into 40%, pH value 8.5.
The preparation method embodiment 3 of water-base epoxy ester resin
（1）According to quality described in 3 embodiment of table, 3 each raw material, in the case where temperature of reaction system is 125 DEG C of reflux states, by vinyl
The mixed liquor of monomer and initiator 1, the mixed solution of epoxy-ester prepolymer A3 and cosolvent 1 is added drop-wise to 290kg/h speed
In, after being added dropwise to complete, insulation reaction 1.5h, then with 240kg/h speed dropwise addition initiator 2 and the mixed solution of cosolvent 2, drop
After the completion of adding, insulation reaction 1.5h, 60 DEG C are cooled to, obtains acrylic modified epoxy ester resin；
（2）According to quality described in 3 embodiment of table, 3 each raw material, in step（1）In being added in gained acrylic modified epoxy ester resin
And agent, after stirring, add water, obtain water-base epoxy ester resin B 3.
After testing, step（1）The acid number of gained acrylic modified epoxy ester resin is 32mgKOH/g, and solid is divided into
80.3%；Step（2）The solid of gained water-base epoxy ester resin B 3 is divided into 40%, pH value 8.5.
The glass transition temperature of water-soluble epoxy ester Resin Example 1~3 and commercially available water-base epoxy ester resin, storage is stable
Property, varnish salt spray resistance are detected, as a result as shown in table 4.
The performance test results table of 4 water-base epoxy ester Resin Example of table 1~3
As shown in Table 4, glass transition temperature >=67 DEG C of water-base epoxy ester Resin Example 1~3 of the present invention, resisting salt fog corrosion time
>=168h, bin stability >=12 month, combination property are better than commercially available water-base epoxy ester resin, illustrate water-base epoxy ester of the present invention
Resin all increases significantly on glass transition temperature, antiseptic property and bin stability.
Claims (10)
1. a kind of epoxy-ester prepolymer, it is characterised in that shunk comprising bisphenol A epoxide resin, dicyclopentadiene dimethanol two
Glycerin ether, terpinum diglycidyl ether, drying oil fatty acid, semi-drying oil aliphatic acid, saturated fat acid anhydrides, unsaturated fat
Acid anhydrides, esterification catalyst and organic solvent.
2. epoxy-ester prepolymer according to claim 1, it is characterised in that the parts by weight of each component are：Bisphenol-A epoxy
155~175 parts of resin, 10~30 parts of dicyclopentadiene dimethanol diglycidyl ether, terpinum diglycidyl ether 10~
30 parts, it is 95~105 parts of drying oil fatty acid, 95~105 parts of semi-drying oil aliphatic acid, 1~5 part of saturated fat acid anhydrides, unsaturated
1~3 part of fatty acid anhydride, 0.10~0.30 part of esterification catalyst, 170~210 parts of organic solvent.
3. epoxy-ester prepolymer according to claim 1 or claim 2, it is characterised in that：The bisphenol A epoxide resin be E-51 types,
One or more in E-44 types, E-20 types or E-12 type epoxy resin；The drying oil fatty acid is linoleic acid, linseed oil
One or both of acid, eleostearic acid, high iodine number ready denier oil acid or dehydrated castor oil fatty acid；The semi-drying oil fat
Acid is soya fatty acid and/or low iodine number ready denier oil acid；The saturated fat acid anhydrides is HHPA, methyl hexahydrobenzene
One or more in acid anhydride or carbic anhydride；The unsaturated fat acid anhydrides is maleic anhydride and/or fumaric acid anhydride；The ester
It is zinc oxide or normal-butyl tin oxide to change catalyst；The organic solvent is propylene glycol monomethyl ether, propylene glycol propyl ether or propane diols fourth
One or more in ether.
A kind of 4. preparation method of the epoxy-ester prepolymer as described in one of claims 1 to 3, it is characterised in that：By bisphenol-A epoxy
Resin, dicyclopentadiene dimethanol diglycidyl ether, terpinum diglycidyl ether, drying oil fatty acid and semi-drying oil
Aliphatic acid mix, carry out first time heating response, after cooling, add saturated fat acid anhydrides, unsaturated fat acid anhydrides and
Esterification catalyst mixes, and carries out second of heating response, cooling, is eventually adding organic solvent,.
5. the preparation method of epoxy-ester prepolymer according to claim 4, it is characterised in that：The first time heating response
Temperature is 180~200 DEG C, and the time is 1~3h；After first time heating response, 145~155 DEG C are cooled to；Second of heating
The temperature of reaction is 190~210 DEG C, is reacted untill acid number≤10mgKOH/g；After second of heating response, 80 are cooled to~
100℃。
A kind of 6. water-base epoxy ester resin, it is characterised in that：Include one of vinyl monomer, initiator, claims 1 to 3 institute
State epoxy-ester prepolymer, cosolvent, nertralizer and water.
7. water-base epoxy ester resin according to claim 6, it is characterised in that the parts by weight of each component are：Vinyl
One of 200~260 parts of monomer, 18~26 parts of initiator, claims 1 to 3 500~550 parts of the epoxy-ester prepolymer, hydrotropy
95~105 parts of agent, 10~20 parts of nertralizer, 770~790 parts of water.
8. according to the water-base epoxy ester resin of claim 6 or 7, it is characterised in that：The vinyl monomer include styrene,
Methacrylic acid, methyl methacrylate, polyethylene glycol methacrylate-styrene polymer and the vinyl monomer of nitro substitution, what it was mixed
Mass ratio is 96~126:12~38:45~75:21~39:6~12；In the polyethylene glycol methacrylate-styrene polymer, poly- second two
The relative molecular weight of alcohol segment is 300~800；The vinyl monomer of the nitro substitution is 2- methyl -2- nitropropyl methyl
Acrylate and/or p-nitrophenyl ethene；The initiator is benzoyl peroxide, peroxybenzoate or peroxide
Change the one or more in lauroyl；The cosolvent is isopropanol, n-butanol, propylene glycol monomethyl ether, propylene glycol propyl ether, propane diols
One or more in butyl ether, dipropylene or methyl iso-butyl ketone (MIBK)；The nertralizer is ammoniacal liquor, triethylamine, dimethyl
One or more in monoethanolamine or meglumine.
9. a kind of preparation method of the water-base epoxy ester resin as described in one of claim 6~8, it is characterised in that including following
Step：
（1）Under reaction system reflux state, by vinyl monomer and the mixed liquor of a part of initiator, claim is added drop-wise to
In the mixed solution of one of 1~3 epoxy-ester prepolymer and a part of cosolvent, after being added dropwise to complete, insulation reaction, then be added dropwise
The mixed solution of remainder initiator and remainder cosolvent, after being added dropwise to complete, insulation reaction, cooling, obtain acrylic acid and change
Property epoxy ester resin；
（2）In step（1）Nertralizer is added in gained acrylic modified epoxy ester resin, after stirring, adds water, obtains water-based ring
Oxygen ester resin.
10. the preparation method of water-base epoxy ester resin according to claim 9, it is characterised in that：Step（1）In, described time
The temperature of stream is 110~130 DEG C；The speed being added dropwise twice is 200~300kg/h；Twice the time of insulation reaction be 1~
2h；The mass ratio for the initiator being successively added dropwise is 3.5~4.5:1；The remainder initiator and remainder cosolvent
Mass ratio is 1:6~12；It is cooled to 50~60 DEG C.
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| CN112029368A (en) * | 2020-09-08 | 2020-12-04 | 湘江涂料科技有限公司 | Bottom-surface-in-one type water-based epoxy ester coating for tower crane standard part and preparation method thereof |
| CN113980539A (en) * | 2021-11-16 | 2022-01-28 | 湘江涂料科技有限公司 | Low-gloss water-based epoxy ester coating for steel structure and preparation method thereof |
| EP4230668A1 (en) * | 2022-02-22 | 2023-08-23 | DIC Corporation | Epoxy ester resin, vinyl-modified epoxy ester resin, resin composition, paint, and article coated with the paint |
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| CN112029368A (en) * | 2020-09-08 | 2020-12-04 | 湘江涂料科技有限公司 | Bottom-surface-in-one type water-based epoxy ester coating for tower crane standard part and preparation method thereof |
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| CN113980539A (en) * | 2021-11-16 | 2022-01-28 | 湘江涂料科技有限公司 | Low-gloss water-based epoxy ester coating for steel structure and preparation method thereof |
| CN113980539B (en) * | 2021-11-16 | 2022-05-03 | 湘江涂料科技有限公司 | Low-gloss water-based epoxy ester coating for steel structure and preparation method thereof |
| EP4230668A1 (en) * | 2022-02-22 | 2023-08-23 | DIC Corporation | Epoxy ester resin, vinyl-modified epoxy ester resin, resin composition, paint, and article coated with the paint |
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Denomination of invention: Epoxy ester prepolymer, preparation method, waterborne epoxy ester resin and method for preparation Effective date of registration: 20230731 Granted publication date: 20200417 Pledgee: Agricultural Bank of China Limited Changsha Wangcheng District sub branch Pledgor: XIANGJIANG PAINT TECHNOLOGY CO.,LTD. Registration number: Y2023980050457 |